CN111057179B

CN111057179B - High-dispersity environment-friendly pure acrylic emulsion for painting materials and preparation method and application thereof

Info

Publication number: CN111057179B
Application number: CN201911406660.9A
Authority: CN
Inventors: 杨灿; 李鸿坚; 唐铖
Original assignee: Anders New Materials Zhongshan Co ltd
Current assignee: Anders New Materials Zhongshan Co ltd
Priority date: 2019-12-31
Filing date: 2019-12-31
Publication date: 2021-11-16
Anticipated expiration: 2039-12-31
Also published as: CN111057179A

Abstract

本公开提供了一种用于画材的高分散性环保型纯丙乳液及其制备方法和用途，涉及精细化工与材料技术领域。所得乳液与水性色浆混合即可用作画材，不仅满足基本性能要求，且具有高分散性、附着力、展色性，且环保性高，符合欧美欧美的环保防腐体系标准。所述乳液由以下组分制备而成：复合单体，乳化剂，引发剂，叔丁基过氧化氢‑亚硫酸氢钠，去离子水，防腐剂，pH调节剂；其中，乳化剂包含磷酸酯型阴离子乳化剂与非离子乳化剂；复合单体包含烷氧基硅烷、(甲基)丙烯酸C_1‑8烷基酯、(甲基)丙烯酸和不饱和单体，所述不饱和单体不同于烷氧基硅烷、(甲基)丙烯酸C_1‑8烷基酯、(甲基)丙烯酸。The present disclosure provides a highly dispersive environment-friendly pure acrylic emulsion for painting materials, a preparation method and application thereof, and relates to the technical fields of fine chemicals and materials. The obtained emulsion can be mixed with water-based color paste and can be used as a painting material, which not only meets the basic performance requirements, but also has high dispersibility, adhesion, color development, and high environmental protection, which conforms to the environmental protection and anti-corrosion system standards in Europe and the United States. The emulsion is prepared from the following components: composite monomer, emulsifier, initiator, tert-butyl hydroperoxide-sodium bisulfite, deionized water, preservative, pH adjuster; wherein, the emulsifier comprises phosphoric acid Ester-type anionic emulsifier and non-ionic emulsifier; composite monomer comprises alkoxysilane, (meth)acrylic acid C _1-8 alkyl ester, (meth)acrylic acid and unsaturated monomer, the unsaturated monomer Different from alkoxysilanes, C _1-8 alkyl (meth)acrylates, (meth)acrylic acid.

Description

High-dispersity environment-friendly pure acrylic emulsion for painting materials and preparation method and application thereof

Technical Field

The invention belongs to the technical field of fine chemical engineering and materials, relates to a pure acrylic emulsion for painting materials, and particularly relates to a high-dispersity environment-friendly pure acrylic emulsion for the painting materials, and a preparation method and application thereof.

Background

The styrene-acrylic emulsion is a mixture prepared by taking styrene and an acrylate monomer as raw materials.

The pure acrylic emulsion is a mixture prepared by taking methyl methacrylate, butyl acrylate, an initiator and an emulsifier as raw materials.

The emulsion used by the painting material adopts emulsion used in the interior and exterior wall coatings in the building industry. The requirements of the interior and exterior wall coatings are that the coatings have excellent scrubbing resistance, chalking resistance, water resistance, alkali resistance, wear resistance, flatness and smoothness. Besides the basic performance requirements, the emulsion for painting materials also meets the performance requirements such as adhesion, water resistance, dispersibility, color development, weather resistance and the like.

For example, patent application No. CN201010278991.1 discloses a styrene-acrylic emulsion for canvas paint, which is prepared from styrene, (meth) acrylic acid monomers and (meth) acrylate monomers as raw materials.

The water-based environment-friendly painting industry belongs to a very subdivided field, modern children pursue DIY fun, and the painting doodling toy is popular, has high requirements on product adhesive force, color brightness and the like, and has very strict requirements on environment-friendly indexes.

The prior product generally adopts styrene-acrylic emulsion for common architectural coating as a main adhesive, and because the styrene contains trace styrene, the final emulsion product contains a small amount of benzene series, and can not meet the export requirement of Europe and America. And a large amount of additives are added in the later period to improve the dispersibility so as to meet the product performance requirement, but the adhesive force and the water resistance of the product are greatly reduced.

For example, patent application with application number of CN2015105761003 discloses a nano color paste for painting material and a manufacturing method thereof, which adopts polymerizable emulsifier to synthesize, and synchronously synthesizes with oil-soluble dye to directly prepare the nano color paste; although resin and a dispersing agent are not required to be added additionally, a large amount of cosolvent is adopted in the product design, and the residual monomer content in the product is high.

Although painting material manufacturers have strong requirements on the upstream acrylic emulsion adhesive and the matching of the upstream acrylic emulsion adhesive, the painting material manufacturers do not have the production capacity of the acrylic emulsion adhesive, and the upstream acrylic emulsion companies have less research and investment on subdivision fields.

For the painting industry, especially for children painting industry, the adhesive product of pure acrylic emulsion specially aiming at the market segment in the field is urgently needed to be provided, and the adhesive product can meet the performance requirement and pass the European and American environment-friendly anticorrosion system standard.

Disclosure of Invention

The invention provides a high-dispersity environment-friendly pure acrylic emulsion for painting materials, which meets the standard of environment-friendly anticorrosion systems in Europe and America, meets the performance requirements, and has high dispersity, adhesive force, color development property and environmental friendliness.

The invention provides a high-dispersity environment-friendly pure acrylic emulsion for painting materials, which is prepared from the following components in parts by weight: 40-50 wt% of composite monomer, 1-4 wt% of emulsifier, 0.2-0.3 wt% of initiator, 0.1-0.2 wt% of tert-butyl hydroperoxide-sodium bisulfite with the proportion of 1:1, 50-60 wt% of deionized water, 0.1-0.8 wt% of preservative and 0.5-1.2 wt% of pH regulator;

wherein the emulsifier comprises phosphate ester type anionic emulsifier and nonionic emulsifier shown in the following formula I,

in the formula I, n is any integer of 20-30, and R is C_10-13Straight chain hydrocarbon group of (2), C_10-13The isohydrocarbyl group of (a);

the composite monomer contains alkoxysilane and (meth) acrylic acid C_1-8Alkyl esters, (meth) acrylic acid and unsaturated monomers other than alkoxysilanes, (meth) acrylic acid C_1-8Alkyl ester, (methyl) acrylic acid, the said unsaturated monomer is one or several kinds of acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, lauryl methacrylate, cyclohexyl methacrylate, ureido methacrylate solution;

the antiseptic is one or more of 2-bromo-2-nitro-1, 3-propylene glycol, phenoxyethanol, iodopropynyl butyl carbamate, and 1, 2-benzisothiazolin-3-one.

Further, the initiator is one or more of ammonium persulfate, sodium persulfate and potassium persulfate.

Further, (meth) acrylic acid C_1-8The alkyl ester is one or more of methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate and isooctyl acrylate.

Further, the alkoxysilane is 2 or more than 2 of vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane and gamma- (2, 3-glycidoxy) propyltrimethoxysilane.

Further, the alkoxysilane comprises one or more of vinyltrimethoxysilane and vinyltriethoxysilane and one or more of gamma-methacryloxypropyltrimethoxysilane and gamma- (2, 3-glycidoxy) propyltrimethoxysilane.

Further, the weight ratio of the alkoxy silane is 0.5 wt% to 1 wt%.

Further, in the formula I, n is any integer of 25-30, and R is C_10-13A linear hydrocarbon group of_10-13The isomeric hydrocarbyl group of (a).

Further, the nonionic emulsifier is one or more of allyl fatty alcohol polyoxyethylene ether, linear alkyl fatty alcohol polyoxyethylene ether and isomeric alcohol polyoxyethylene ether.

Further, the phosphate ester type anionic emulsifier is one or more of allyl fatty alcohol polyoxyethylene ether phosphate diester, alcohol ether polyoxyethylene phosphate monoester, high monoester phosphate and methacrylic acid phosphate. Further, the mass ratio of the phosphate ester type anionic emulsifier to the nonionic emulsifier is 1: 1-4.

The invention also provides a preparation method of any one of the high-dispersity environment-friendly pure acrylic emulsion for the painting materials, which is characterized by comprising the following steps of:

1) mixing an emulsifier: neutralizing the phosphate ester type anionic emulsifier with 2-amino-2-methyl-1-propanol, and mixing with a nonionic emulsifier to obtain a mixed emulsifier;

2) preparing an emulsion: adding deionized water into an emulsifying cylinder, adding part of the mixed emulsifier into the water in the emulsifying cylinder, stirring at high speed for dispersing for 10-30 minutes, slowly adding unsaturated monomer and (methyl) acrylic acid, continuing stirring for 10-30 minutes, and then adding (methyl) acrylic acid C_1-880-90 wt% of alkyl ester and alkoxy silane, and stirring for 10-60 minutes for later use;

3) preparing a reaction cylinder bottom material: adding deionized water into the reaction cylinder, heating to 60-70 deg.C, and adding the other part of mixed emulsifier;

4) preparation of initial initiator solution: stirring and dissolving an initiator by using deionized water for later use;

5) preparation of dropwise addition initiator solution: stirring and dissolving an initiator in an initiator cylinder by using deionized water for later use, wherein the mass ratio of the initial initiator to the dropwise added initiator is 2: 8;

6) heating the materials in the reaction cylinder to 80-90 ℃, adding 2-10 wt% of emulsion into the reaction cylinder, then adding a primary initiator solution, reacting for 15-40 minutes, and after the emulsion in the reaction cylinder turns blue, simultaneously dropwise adding the rest emulsion and the initiator solution into the reaction cylinder at a constant speed; the dropping time is 180-300 minutes, and the temperature is 82-90 ℃;

7) after the dropwise addition is finished, keeping the temperature of the reaction cylinder at 85-88 ℃ and maintaining the reaction for 60 minutes;

8) respectively preparing a tert-butyl hydroperoxide solution and a sodium bisulfite solution by using 5 percent deionized water;

9) reducing the temperature of the reaction cylinder to 65-70 ℃, then simultaneously dropwise adding a tert-butyl hydroperoxide solution and a sodium bisulfite solution, keeping the temperature at 66-70 ℃, and dropwise adding for 90 minutes;

10) the temperature of the emulsion in the reaction cylinder is reduced to 40-45 ℃, the pH is adjusted to 7-9, the mixture is stirred for 15 minutes, then the preservative solution is added, and finally the rest alkoxy silane is added.

Further, the unsaturated monomer comprises two parts, wherein one part is one or more of acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, and the other part is one or more of lauryl methacrylate, cyclohexyl methacrylate and ureido methacrylate solution;

in the step 2), adding deionized water into an emulsifying cylinder, putting part of the mixed emulsifier into the water in the emulsifying cylinder, stirring at a high speed for dispersing for 10-30 minutes, slowly adding one or more of acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate and (methyl) acrylic acid, continuously stirring for 10-30 minutes, and then adding (methyl) acrylic acid C_1-880-90 wt% of alkyl ester and alkoxy silane, and stirring for 10-60 minutes for later use;

step 6), heating the materials in the reaction cylinder to 80-90 ℃, adding 2-10 wt% of emulsion into the reaction cylinder, then adding a primary initiator solution, reacting for 15-40 minutes, and after the emulsion in the reaction cylinder turns blue, simultaneously dropwise adding the rest emulsion, the initiator solution and the other part of unsaturated monomers into the reaction cylinder at a constant speed; the dropping time is 180-300 minutes and the temperature is 82-90 ℃.

Further, the alkoxysilane comprises one or more of vinyltrimethoxysilane and vinyltriethoxysilane and one or more of gamma-methacryloxypropyltrimethoxysilane and gamma- (2, 3-glycidoxy) propyltrimethoxysilane;

adding one or more of vinyltrimethoxysilane and vinyltriethoxysilane in the step 2); in the step 10), one or more of gamma-methacryloxypropyltrimethoxysilane and gamma- (2, 3-glycidoxy) propyltrimethoxysilane are added.

The invention also provides the application of any one of the high-dispersity environment-friendly pure acrylic emulsion for the painting materials in the painting materials, and the emulsion is mixed with the water-based color paste.

The invention provides a high-dispersity environment-friendly acrylic emulsion for painting materials, a preparation method and application thereof.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The embodiment of the invention provides a high-dispersity environment-friendly pure acrylic emulsion for painting materials, which is prepared from the following components: 40-50 wt% of composite monomer, 1-4 wt% of emulsifier, 0.2-0.3 wt% of initiator, 0.1-0.2 wt% of tert-butyl hydroperoxide-sodium bisulfite with the proportion of 1:1, 50-60 wt% of deionized water, 0.1-0.8 wt% of preservative and 0.5-1.2 wt% of pH regulator;

The high-dispersity environment-friendly acrylic emulsion for the painting materials, provided by the embodiment of the invention, conforms to the standard of European and American environment-friendly anticorrosion systems, meets the performance requirements, and has high dispersity, adhesion, color development and environmental friendliness.

Suitable initiators may be one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

Suitable pH regulator can be one or more of ammonia water, sodium hydroxide, ethanolamine, and 2-amino-2-methyl-1-propanol (AMP-95).

In the pure acrylic emulsion of the invention, the composite monomer comprises alkoxy silane and (methyl) acrylic acid C_1-8Alkyl esters, (meth) acrylic acid, and unsaturated monomers. Different monomers have different properties, and the (meth) acrylic acid C suitable for adjusting the monomers to adjust the product to meet the performance requirements of the product_1-8The alkyl ester can be one or more of methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate and isooctyl acrylate.

The alkoxy silane can be 2 or more than 2 of vinyl trimethoxy silane, vinyl triethoxy silane, gamma-methacryloxypropyl trimethoxy silane and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane.

Suitable alkoxysilanes may include one or more of vinyltrimethoxysilane and vinyltriethoxysilane and one or more of gamma-methacryloxypropyltrimethoxysilane and gamma- (2, 3-glycidoxy) propyltrimethoxysilane.

Further, the weight ratio of the alkoxysilane may be 0.5 wt% to 1 wt%.

The influence of the crosslinking density on the adhesion of emulsion products is large, the adhesion is better when the crosslinking density is large, however, the adhesion is reduced when the crosslinking density is too large. Compared with the conventional monomer, the composite monomer of the invention distinguishes the performances of each monomer, combines the characteristics of the monomers and the polarity of the main monomer, and improves the adhesion performance.

For improving the adhesion and dispersion properties, suitable nonionic emulsifiers can be those of the formula I,

in the formula I, n is any integer of 20-30, and R is C_10-13Straight chain hydrocarbon group of (2), C_10-13The isohydrocarbyl group of (1).

Further, in the formula I, n is any integer of 25-30, and R is C_10-13Straight chain hydrocarbon group of (2), C_10-13The isomeric hydrocarbyl group of (a). Further, in the formula I, n is any integer of 25-30, and R is C₁₃Straight chain hydrocarbon group of (2), C₁₃The isomeric hydrocarbon group of (1), the linear hydrocarbon group may be, for example, a linear alkyl group, an alkenylalkyl group; the isomeric hydrocarbyl groups may be isomeric alkyl groups.

Further, the applicable nonionic emulsifier can be one or more of allyl fatty alcohol polyoxyethylene ether, linear alkyl fatty alcohol polyoxyethylene ether and isomeric alcohol polyoxyethylene ether. Examples are allyl fatty alcohol polyoxyethylene ether (n ═ 25), allyl fatty alcohol polyoxyethylene ether (n ═ 30), isomeric tridecanol polyoxyethylene ethers (n ═ 25), isomeric tridecanol polyoxyethylene ethers (n ═ 30), and the like.

Further, the suitable phosphate ester type anionic emulsifier is one or more of allyl fatty alcohol polyoxyethylene ether phosphate diester, alcohol ether polyoxyethylene phosphate monoester, high monoester phosphate and methacrylic acid phosphate. The applicable emulsifier does not contain APEO and has environmental protection performance.

The phosphate ester type anionic emulsifier is neutralized into salt by using 2-amino-2-methyl-1-propanol before use.

Further, the mass ratio of the phosphate ester type anionic emulsifier to the nonionic emulsifier is 1: 1-4.

According to the styrene-acrylic emulsion disclosed by the embodiment of the invention, the special polymerizable phosphate emulsifier and the special crosslinking monomer are adopted for modification polymerization, so that the adhesion force of the pure acrylic emulsion on a base material and the high dispersibility of the pure acrylic emulsion on color paste can be greatly improved, the styrene-acrylic emulsion can play excellent wetting and dispersing properties after the color paste is added, the styrene-acrylic emulsion can depend on the excellent self-dispersing property of phosphate groups on a molecular chain of the pure acrylic emulsion without additionally adding wetting and dispersing agents, and the styrene-acrylic emulsion can be quickly wetted to the color paste by virtue of the high-efficiency nonionic emulsifier in the emulsion, so that the requirements of high color development property and extremely low color difference value are met.

An embodiment of the present invention further provides a preparation method of any one of the above high-dispersibility environment-friendly acrylic emulsion for painting materials, which may include the following steps:

In a preferred embodiment, the unsaturated monomer is divided into two parts according to polarity in order to improve dispersibility and color developability. Specifically, one part is one or more of acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, and the other part is one or more of lauryl methacrylate, cyclohexyl methacrylate and ureido methacrylate solution. In the process of preparing the pure acrylic emulsion, the two unsaturated monomers are separately and independently dropwise added. One part is added in the preparation of the emulsion in step 2), and the other part is added simultaneously with the rest of the emulsion and the dropwise addition of the initiator in step 6).

The first part of unsaturated monomers are one or more of acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, the polarity of the unsaturated monomers is close to that of other main monomers, the unsaturated monomers have stronger hydrophilicity and are easy to emulsify, and the unsaturated monomers can be emulsified together with other composite monomer components; the other part of unsaturated monomers are one or more of lauryl methacrylate, cyclohexyl methacrylate and ureido methacrylate solutions, the polarity of the unsaturated monomers is greatly different from that of other monomers, uniform pre-emulsion cannot be formed, and the unsaturated monomers cannot be well polymerized and evenly distributed on a main chain in the synthesis process and are easy to generate self-polymerization.

Specifically, in the step 2), deionized water is added into an emulsification cylinder, part of mixed emulsifier is added into water in the emulsification cylinder, high-speed stirring and dispersion are carried out for 10-30 minutes, and then part of unsaturated monomers (acrylamide and hydroxyethyl methacrylate) are slowly addedOne or more of hydroxyethyl acrylate and hydroxypropyl acrylate) and (methyl) acrylic acid, continuously stirring for 10-30 min, and adding (methyl) acrylic acid C_1-880-90 wt% of alkyl ester and alkoxy silane, and stirring for 10-60 minutes for later use;

in the step 6), heating the materials in the reaction cylinder to 80-90 ℃, adding 2-10 wt% of emulsion into the reaction cylinder, then adding an initial initiator solution, reacting for 15-40 minutes, after the emulsion in the reaction cylinder turns blue, simultaneously dropwise adding the rest emulsion, the initiator solution and one or more of unsaturated monomers (lauryl methacrylate, cyclohexyl methacrylate and ureido methacrylate) into the reaction cylinder at a constant speed; the dropping time is 180-300 minutes and the temperature is 82-90 ℃.

Further, in order to optimize the characteristics of the composite monomer combination, the alkoxy silane comprises one or more of vinyl trimethoxy silane and vinyl triethoxy silane and one or more of gamma-methyl acrylic acyloxy propyl trimethoxy silane and gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane; one part is added in step 2) and the other part is added in step 10).

Specifically, one or more of vinyltrimethoxysilane and vinyltriethoxysilane are added in the step 2); in the step 10), one or more of gamma-methacryloxypropyltrimethoxysilane and gamma- (2, 3-glycidoxy) propyltrimethoxysilane are added.

In the preparation method provided by the embodiment of the invention, the special polymerizable phosphate emulsifier and the special crosslinking monomer are adopted for modification polymerization, so that the adhesive force of the acrylic emulsion on the base material and the high dispersibility of the acrylic emulsion to the color paste can be greatly improved, the acrylic emulsion can play excellent wetting and dispersing properties after the color paste is added, the acrylic emulsion can depend on the excellent self-dispersing property of the phosphate group on the molecular chain of the acrylic emulsion without additionally adding wetting and dispersing agents, and the acrylic emulsion can be quickly wetted to the color paste by the high-efficiency nonionic emulsifier in the emulsion, so that the requirements of high color developability and extremely low color difference value are met.

The reactivity ratio of the special functional monomer is different from that of the conventional monomer, the water phase dispersion in an emulsifying cylinder easily causes the defects of activity reduction and uneven dispersion, a unique separate and synchronous dripping mode with an emulsion is adopted in the preparation, a separate dripping mode is also adopted between the monomer and the monomer, the unsaturated monomer is divided into two parts according to the polarity and is separately dripped, the problems of slag formation, emulsion breaking and other instability in the product synthesis process can be solved, and the adhesive force performance of the product to a base material, the color development performance and the like are improved.

The preparation method provided by the embodiment of the invention has less residue of harmful substances such as benzene series, formaldehyde and the like, meets the requirements of the limit values in the regulations of EN71 and EUH-208, and meets the standards of European and American exports.

The preparation method provided by the embodiment of the invention has good product stability and dispersibility.

The embodiment of the invention also provides the application of any one of the high-dispersity environment-friendly pure acrylic emulsion for the painting materials in the painting materials, and the emulsion can be used as the painting materials after being mixed with the water-based color paste.

The following describes in detail the high-dispersibility environment-friendly acrylic emulsion for painting materials, and the preparation method and use thereof with specific examples.

Example 1

Composition and proportion

The high-dispersity environment-friendly pure acrylic emulsion is prepared from the following raw materials in parts by weight: methyl methacrylate: 15 percent; n-butyl acrylate: 15 percent; isooctyl acrylate: 10 percent; acrylic acid: 0.6 percent; hydroxyethyl acrylate: 0.8 percent; ureido methacrylate: 0.5 percent; vinyl trimethoxy silane: 0.8 percent; mixing an emulsifier: 1.5 percent; the proportion of the anionic emulsifier and the nonionic emulsifier is as follows: 1: 1; anionic emulsification is: the nonionic emulsifier is isomeric alcohol polyoxyethylene ether (isomeric tridecanol polyoxyethylene ether); the total amount of the initial initiator and the dropwise initiator is potassium persulfate: 0.3 percent; the distribution of the initial initiator and the dropwise initiator is as follows: 2: 8; tert-butyl hydroperoxide-sodium bisulfite with the proportion of 1:1 and the proportion of 0.2 percent; the preservative adopts phenoxyethanol, and the using amount is 0.8%; AMP-95: the using amount is 1 percent; then gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (A-187) is added to be 0.1 percent; the deionized water content was 53.4%.

Preparation of

Preparing an emulsion: adding deionized water accounting for 30% of the total amount into an emulsification cylinder, putting 60% of the neutralized mixed emulsifier into water in the emulsification cylinder, stirring at a high speed for 30 minutes, slowly adding acrylic acid and hydroxyethyl acrylate, continuing stirring for 15 minutes, then adding methyl methacrylate, n-butyl acrylate, isooctyl acrylate and vinyltrimethoxysilane, and stirring for 30 minutes for standby.

Preparing a reaction cylinder bottom material: adding deionized water accounting for 45 percent of the total amount into the reaction cylinder, heating to 65 ℃ in the kettle, and adding 40 percent of the neutralized mixed emulsifier.

Preparation of initial initiator solution: the initiator added initially is stirred and dissolved by 5 percent deionized water for later use.

Preparation of dropwise addition initiator solution: and stirring and dissolving the dropwise added initiator in an initiator cylinder by using 10% deionized water for later use.

Heating the materials in the reaction cylinder to 86-88 ℃, adding 5% of the prepared emulsion into the reaction cylinder, adding the prepared initial initiator solution, reacting for 20 minutes, and after the emulsion in the reaction cylinder becomes blue stable, simultaneously dropwise adding the rest emulsion, the initiator solution and the ureido methacrylate solution into the reaction cylinder at a constant speed; the dropping time is 240 minutes; the temperature is controlled between 86 and 90 ℃.

After the completion of the dropwise addition, the temperature of the reaction vessel was kept at 85 to 88 ℃ and the reaction was maintained for 60 minutes.

A solution of t-butyl hydroperoxide and a solution of sodium bisulfite were prepared with 5% deionized water, respectively.

The temperature of the reaction cylinder is reduced to 65-70 ℃, and then the tert-butyl hydroperoxide solution and the sodium bisulfite solution are simultaneously dripped, the temperature is kept at 66-70 ℃, and the dripping time is 90 minutes.

Reducing the temperature of the emulsion in the reaction cylinder to 40-45 ℃, adjusting the pH value to 7-9, stirring for 15 minutes, then adding phenoxyethanol solution, finally adding 0.1% gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane (A-187), then filtering with a 300-mesh filter bag and discharging.

Example 2

Composition and proportion

The high-dispersity environment-friendly pure acrylic emulsion is prepared from the following raw materials in parts by weight: methyl methacrylate: 15 percent; n-butyl acrylate: 15 percent; isooctyl acrylate: 10 percent; acrylic acid: 0.6 percent; acrylamide: 0.8 percent; ureido methacrylate: 0.5 percent; vinyltrimethoxysilane: 0.8 percent; mixing an emulsifier: 1.5 percent; the proportion of the anionic emulsifier and the nonionic emulsifier is as follows: 1: 1; anionic emulsification is: allyl fatty alcohol polyoxyethylene ether phosphate diester, and the nonionic emulsifier is fatty alcohol polyoxyethylene ether; the primary initiator and the dropwise initiator are potassium persulfate: 0.3 percent; the distribution of the initial initiator and the dropwise initiator is as follows: 2: 8; tert-butyl hydroperoxide-sodium bisulfite with the proportion of 1:1 and the proportion of 0.2 percent; the preservative adopts phenoxyethanol, and the using amount is 0.8%; AMP-95: the using amount is 1 percent; then gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (A-187) is added to be 0.1 percent; the deionized water content was 53.4%.

Preparation of

Preparing an emulsion: adding deionized water 30% of the total amount into an emulsifying cylinder, adding 60% of the neutralized and mixed emulsifier into the water in the emulsifying cylinder, stirring at high speed for 30 minutes, slowly adding acrylic acid and hydroxyethyl acrylate, continuing stirring for 15 minutes, then adding methyl methacrylate, n-butyl acrylate, isooctyl acrylate, vinyl trimethoxy silane and urea methacrylate, and stirring for 30 minutes for later use.

Heating the materials in the reaction cylinder to 86-88 ℃, adding 5% of the prepared emulsion into the reaction cylinder, adding the prepared initial initiator solution, reacting for 20 minutes, and after the emulsion in the reaction cylinder becomes blue stable, simultaneously dropwise adding the rest emulsion and the initiator solution into the reaction cylinder at a constant speed; the dropping time is 240 minutes; the temperature is controlled between 86 and 90 ℃.

The procedure is as in example 1, except that the ureido methacrylate is not added dropwise separately.

Example 3

Composition and proportion

The high-dispersity environment-friendly pure acrylic emulsion is prepared from the following raw materials in parts by weight: methyl methacrylate: 13 percent; ethyl acrylate: 17 percent; isooctyl acrylate: 10 percent; methacrylic acid: 0.6 percent; acrylamide: 0.6 percent; cyclohexyl methacrylate: 1.0 percent; vinyl trimethoxysilane: 0.8 percent; mixing an emulsifier: 2 percent; the proportion of the anionic emulsifier and the nonionic emulsifier is as follows: 1: 2.5; anionic emulsification is: methacrylic acid phosphate ester, and the nonionic emulsifier is isomeric alcohol polyoxyethylene ether; the primary initiator and the dropwise initiator are potassium persulfate: 0.3 percent; the distribution of the initial initiator and the dropwise initiator is as follows: 2: 8; tert-butyl hydroperoxide-sodium bisulfite with the proportion of 1:1 and the proportion of 0.2 percent; the preservative is 2-bromo-2-nitro-1, 3-propanediol (Brobopol), and the using amount is 0.8%; AMP-95: the dosage is as follows: 1 percent; the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (A-187) is added to be 0.1 percent; the deionized water content was 53.4%.

The preparation process is as in example 1, the cyclohexyl methacrylate and acrylamide are added dropwise separately and together with the remaining emulsion and the dropwise addition initiator solution.

Example 4

Composition and proportion

The high-dispersity environment-friendly pure acrylic emulsion is prepared from the following raw materials in parts by weight: methyl acrylate: 20 percent; n-butyl methacrylate: 10 percent; isooctyl acrylate: 10 percent; methacrylic acid: 0.6 percent; hydroxypropyl acrylate: 0.8 percent; lauryl methacrylate: 0.5 percent; vinyl triethoxysilane: 0.8 percent; mixing an emulsifier: 1.5 percent; the proportion of the anionic emulsifier and the nonionic emulsifier is as follows: 1: 3; anionic emulsification is: the ratio of the alcohol ether polyoxyethylene phosphate monoester to the methacrylic acid phosphate ester is 1:1, and the nonionic emulsifier is allyl fatty alcohol polyoxyethylene ether; the primary initiator and the dropwise initiator are potassium persulfate: 0.3 percent; the distribution of the initial initiator and the dropwise initiator is as follows: 2: 8; the post-treatment initiator is: tert-butyl hydroperoxide-sodium bisulfite with the proportion of 1:1 and the proportion of 0.2 percent; the preservative adopts iodopropynyl butyl carbamate (IPBC), and the dosage is as follows: 0.8 percent; pH value regulator: AMP-95: the using amount is 1 percent; the deionized water was 56.5%.

The preparation method was the same as in example 1, and lauryl methacrylate and hydroxypropyl acrylate were added dropwise separately, together with the remaining emulsion and dropwise addition of the initiator solution.

And (3) later-stage blending and testing:

as no test method specially aiming at the dispersion and the adhesive force of the painting materials exists, according to the actual experience and the comparative test method used by the actual customers, the high-dispersion environment-friendly pure acrylic emulsion prepared in the embodiment 1-4 is respectively added with 2% of water-based color pastes with different colors according to 100% of emulsion, and after the mixture is uniformly stirred, the performance and the adhesive force of the ABS transparent plastic plate are tested by referring to the method of GB/T9286-1998 paint film coating adhesive force test.

Referring to a test method of color paste for GB/T21473-2008 color mixing system-appendix A, adding 4 water-based color paste samples with different colors (carbon black, iron red, phthalocyanine blue and iron yellow) on a standard white paper card by using a colorimeter for comparison test, wherein the color difference value (delta E value) before and after grinding is used for evaluating the dispersion performance and color development performance difference of the acrylic emulsion to the color paste by judging the compatibility of the color paste.

Environmental protection index test-total of residual monomers: the test is carried out by referring to the standard test method of GB/T20623 & 2006 appendix A & gt emulsion for architectural coatings.

The method for testing the content of the residual formaldehyde comprises the following steps: the test is carried out by referring to a standard test method of GB 18583 Amplifier 2008 indoor decoration material-appendix A for limiting harmful substances in the adhesive.

Benzene series test: the test is carried out by referring to a standard test method of GB18582-2008 indoor decoration material-appendix A for limiting harmful substances in the interior wall coating.

Testing of total volatile organic content of TVOC: the test is carried out by referring to a standard test method of GB 18583 Amplifier 2008 indoor decoration material-appendix F for limiting harmful substances in adhesive.

Phthalate plasticizer test: the test was carried out according to the test method described in GB/T22048-2015, the toy and the determination of the plasticizer of the specific phthalate esters in the children's products.

Preservative testing: reference is made to the European Union "EN 71-9: 2005 organic compound Limit and EUH208 Risk Tab.

And (3) performing a product microorganism challenge experiment, referring to a CTFA cosmetic corrosion resistance challenge experiment and an evaluation standard, performing 5 rounds of challenge experiment results in a strain adding mode, and then judging.

And (3) testing results:

the styrene-acrylic emulsion (commonly used non-phosphate ester emulsifier) for the architectural coating used for the painting products with general requirements is collected on the surface of the comparison sample 1 (Pasteur styrene-acrylic emulsion 7035), and the comparison test is carried out under the same condition and the same time.

The test result shows that: the adhesive force is tested by adopting a Baige method, the adhesive force of the embodiment 1 and the embodiment 4 has good adhesive force, the test of a comparison sample on an ABS plate (acrylonitrile/butadiene/styrene copolymer plate) shows that the adhesive force is general, and the result analysis has great direct influence on the use and addition scheme of the functional monomer of the product and the subsequent addition of A-187 to further promote the adhesive force to be improved; generally, the color difference value delta E is considered to be between 0 and 0.25, the color development performance is judged to be excellent, and the color development performance is recommended to be suitable for the water-based painting material product; the delta E value is between 0 and 0.25, the color development performance is judged to be general, and the color developing agent can be used in water-based painting products; when the delta E value is more than 0.5, the color-spreading property is judged to be slightly poor, and the color-spreading agent is not suitable for being applied to water-based painting materials; from the analysis of examples 1-4 and the comparative sample, the results of the color development test are the best in example 1 and slightly worse in example 2, but the performance is obviously better than that of comparative sample 1 because the phosphate ester type emulsification systems are adopted; in the aspect of environmental protection performance, because the existing relevant legal and legal requirements are considered when the product is invented, in the aspect of environmental protection performance testing, the examples 1 to 4 can pass relevant detection requirements, and can pass bacterial challenge experiments through a screened antiseptic system and a scheme of adding amount, and the influence that the actual production requirements cannot be met does not exist; and the competitive product comparison sample 1 in the market cannot meet the European Union standard in the detection of an antiseptic system, mainly uses the conventional Kathon and BIT preservatives, and the use amount of the detection result exceeds the standard.

And (4) conclusion: the emulsion provided by the embodiment of the invention can be used for synthesizing pure acrylic emulsion completely meeting high dispersibility and environmental protection performance, and is finally applied to high-grade water-based painting products. Among them, the preparation scheme of example 1 is the most preferable.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are illustrative and not to be construed as limiting the present invention, and that variations, modifications, substitutions and alterations in the above embodiments may be made by those skilled in the art without departing from the principle and spirit of the invention. The scope of the invention is defined by the appended claims and equivalents thereof.

The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention, and all such changes or substitutions are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. a kind of high dispersibility environment-friendly pure acrylic emulsion for painting material, is characterized in that, is prepared from the following components: the composite monomer of 40wt%-50wt%, the emulsifier of 1wt%-4wt%, 0.2wt% %-0.3wt% initiator, 0.1%-0.2wt% 1:1 tert-butyl hydroperoxide-sodium bisulfite, 50wt%-60wt% deionized water, 0.1wt%-0.8 wt% preservative, 0.5wt%-1.2wt% pH adjuster;

Wherein, the emulsifier comprises a phosphate type anionic emulsifier and a nonionic emulsifier shown in the following formula I,

In formula I, n is any integer from 20 to 30, and R is a straight-chain hydrocarbon group of C _10-13 or an isomeric hydrocarbon group of C _10-13 ;

The composite monomers comprise alkoxysilanes, C _1-8 alkyl (meth)acrylates, (meth)acrylic acids and unsaturated monomers, the unsaturated monomers being different from alkoxysilanes, (methyl) C _1-8 alkyl acrylate, (meth)acrylic acid;

Described unsaturated monomer comprises one or more in acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and lauryl methacrylate, cyclohexyl methacrylate, methacrylic acid One or more of ureido ester solutions;

The preservative is one of 2-bromo-2-nitro-1,3-propanediol, phenoxyethanol, butyl iodopropynyl carbamate, 1,2-benzisothiazolin-3-one or several.

2. The highly dispersible environment-friendly pure acrylic emulsion for painting material according to claim 1, wherein the alkoxysilane is vinyltrimethoxysilane, vinyltriethoxysilane, γ-methyl Two or more of acryloyloxypropyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane;

(Meth) C _1-8 alkyl acrylate is one or more of methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate and isooctyl acrylate.

3. The highly dispersible environment-friendly pure acrylic emulsion for painting materials according to claim 2, wherein the weight ratio of the alkoxysilane is 0.5wt%-1wt%; the alkoxysilane comprises vinyltrimethoxy One or more of silane and vinyltriethoxysilane and gamma-methacryloyloxypropyltrimethoxysilane and gamma-(2,3-glycidoxy)propyltrimethoxysilane one or more of.

4. The highly dispersive environment-friendly pure acrylic emulsion for drawing material according to claim 1, wherein in formula I, in formula I, n is any integer in the range of 25-30, and R is C _10-13 The straight chain hydrocarbon group, C _10-13 isomeric hydrocarbon group.

5. the highly dispersive environment-friendly pure acrylic emulsion for painting material according to claim 4, is characterized in that, phosphate ester type anionic emulsifier is allyl fatty alcohol polyoxyethylene ether phosphoric acid diester, alcohol ether polyoxygen One or more of ethylene phosphoric acid monoester, high monoester phosphoric acid ester and methacrylic acid phosphoric acid ester.

6 . The highly dispersive environment-friendly pure acrylic emulsion for painting materials according to claim 5 , wherein the mass ratio of the phosphate type anionic emulsifier to the nonionic emulsifier is 1:1-4. 7 .

7. a kind of preparation method of the high dispersibility environment-friendly pure acrylic emulsion that is used for drawing material as described in any one of claim 1-6, is characterized in that, comprises the steps:

1) mixed emulsifier: neutralize phosphate type anionic emulsifier with 2-amino-2-methyl-1-propanol, mix it with nonionic emulsifier to obtain mixed emulsifier;

2) Emulsion preparation: add deionized water to the emulsifying tank, put part of the mixed emulsifier into the emulsifying tank water, stir and disperse at high speed for 10-30 minutes, slowly add unsaturated monomers and (meth)acrylic acid, and continue stirring for 10-30 minutes minutes, then add (meth)acrylic acid C _1-8 alkyl ester, alkoxysilane 80wt%-90wt%, stir for 10-60 minutes for use;

3) Preparation of the bottom material of the reaction cylinder: add deionized water to the reaction cylinder, heat up to 60-70° C. of the temperature in the kettle, and add another part of the mixed emulsifier;

4) Preparation of initial addition of initiator solution: the initiator is stirred and dissolved in deionized water for subsequent use;

5) The preparation of dripping initiator solution: the initiator is stirred and dissolved with deionized water in the initiator cylinder for subsequent use, and the mass ratio of the initial addition of the initiator and the dripped initiator is 2:8-4:6;

6) heating the material in the reaction cylinder to 80-90 ℃, adding 2wt%-10wt% of the emulsion to the reaction cylinder, then adding the initial initiator solution, reacting for 15-40 minutes, after the emulsion in the reaction cylinder turns blue, simultaneously; Add the remaining emulsion and the initiator solution dropwise at a constant speed to the reaction tank; the dropping time is 180-300 minutes, and the temperature is 82-90°C;

7) dripping is completed, the temperature of the reaction cylinder is maintained at 85-88 ° C, and the reaction is maintained for 60 minutes;

8) configure tert-butyl hydroperoxide solution and sodium bisulfite solution with 5% deionized water respectively;

9) reduce the temperature of the reaction tank to 65-70 ℃, then dropwise add tert-butyl hydroperoxide solution and sodium bisulfite solution simultaneously, keep the temperature at 66-70 ℃, and the dropping time is 90 minutes;

10) Lower the temperature of the emulsion in the reaction tank to 40-45°C, adjust the pH to 7-9, stir for 15 minutes, then add the preservative solution, and finally add the remaining alkoxysilane.

8. preparation method according to claim 7 is characterized in that, unsaturated monomer comprises two parts, and one part is one of acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate or Several, the other part is one or more in lauryl methacrylate, cyclohexyl methacrylate, ureido methacrylate solution;

In step 2), deionized water is added to the emulsifying tank, part of the mixed emulsifier is put into the emulsifying tank water, and after high-speed stirring and dispersing for 10-30 minutes, acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxy acrylate are slowly added. One or more of propyl esters and (meth)acrylic acid, continue to stir for 10-30 minutes, then add (meth)acrylic acid C _1-8 alkyl ester, alkoxysilane 80wt%-90wt%, stir for 10 -60 minutes standby;

In step 6), the temperature of the material in the reaction cylinder is raised to 80-90° C., 2wt%-10wt% of the emulsion is added to the reaction cylinder, and then the initial addition of the initiator solution is added, and the reaction is performed for 15-40 minutes, and the emulsion in the reaction cylinder turns blue. Then, the remaining emulsion, the initiator solution, and another part of the unsaturated monomer are added dropwise to the reaction cylinder at a constant speed; the dropping time is 180-300 minutes, and the temperature is 82-90°C.

9 . The preparation method according to claim 7 , wherein the alkoxysilane comprises one or more of vinyltrimethoxysilane and vinyltriethoxysilane and γ-methacryloyloxysilane. 10 . One or more of propyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane;

In step 2), add one or more of vinyltrimethoxysilane and vinyltriethoxysilane; in step 10), add γ-methacryloyloxypropyltrimethoxysilane and γ- One or more of (2,3-glycidoxy)propyltrimethoxysilane.

10. The use of the highly dispersive environment-friendly pure acrylic emulsion for painting materials according to any one of claims 1-6 in painting materials, mixed with water-based color paste.